Synthesis of oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)] and anomalous proton conductivities of the thin films

New proton-conductive polyamide oligomers, oligomeric poly[(1, 2-propanediamine)-alt-(oxalic acid)], were synthesized to investigate the proton transport properties of bulk and thin films. The obtained oligomers were characterized by the X-ray diffraction, FT-IR spectra, ¹H NMR, Matrix Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrum, and electrical conductivity measurements. The bulk proton conductivity is 3.0 × 10^? 4 S cm^? 1 at the relative humidity (RH) of 80%. The proton conductivity of thin film is relatively higher than that of bulk sample. Thickness dependence of the proton conductivity was observed in these thin films. The maximum proton conductivity of the thin film is 4.0 × 10^? 3 S cm^? 1 at the relative humidity (RH) of 80%, which is higher one order magnitude than that of the bulk sample. The activation energies of bulk and 200 nm thick film are 1.0 and 0.69 eV at the RH of 60%, respectively.     

Preparation of poly(vinyl phosphate-b-styrene) copolymers and its blend with PPO as proton exchange membrane for DMFC applications

Poly(vinyl phosphate-b-styrene) (poly(VPP-b-St)) block copolymers were prepared via consecutive telomerization of vinyl acetate (VAc), atom transfer radical polymerization (ATRP) with styrene, saponification, and phosphorylation with phosphorus oxychloride. The resulting block copolymers were characterized by FT-IR and pH titration. Then, the block copolymers were blended with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) to prepare direct methanol fuel cell (DMFC) membrane. The performance of poly(VPP-b-St)/PPO blend membranes was measured in terms of proton conductivity, methanol permeability, thermal and hydrolytic stability. The proton conductivities were in the range of 10^− 4 to 10^− 2 S/cm (60 °C, RH = 95%); the methanol permeabilities were in the range of 4.14 × 10^− 8 to 9.62 × 10^− 8 cm²/s (25 °C), and quite lower than that of Nafion® 117. Also, the thermal stability of the blend membranes was characterized by TGA, and was stable up to 400 °C; the blend membranes had better hydrolytic stability.     

Poly(ethyleneglycol methacrylate phosphate) and heterocycle based proton conducting composite materials

Novel anhydrous proton conducting polymer electrolytes based on poly(ethyleneglycol methacrylate phosphate) (PEGMAP) and heterocycle have been investigated. The materials were synthesized via conventional radical bulk polymerization of ethylene glycol methacrylate phosphate in the presence of proton solvents such as imidazole (Im) or benzimidazole (BnIm). The poly(EGMAP–Im_x) or poly(EGMAP–BnIm_x) composites were produced where x is the molar ratio of heterocycle to monomer in the feed. The polymer–heterocycle electrolytes were characterized by elemental analysis (EA), FT-IR spectroscopy, thermogravimetry analysis (TG), differential scanning calorimetry (DSC) and impedance spectroscopy. Maximum proton conductivity of 2 × 10^− 4 S/cm has been obtained for the anhydrous composite electrolytes at 160 °C.     

Investigation of reduced graphene oxide effects on ultra-violet detection of ZnO thin film

The reduced graphene oxide (rGO) incorporated ZnO thin films were fabricated by dip-coating method. The Raman and FT-IR spectra of 0.075 wt% incorporated composite film showed reduction of GO in composite film. The transmittanceProd. Type: FTP spectra have shown that rGO incorporation increase the visible light absorption of ZnO thin film while the calculated band gaps of samples were decreased from 3.28 to 3.25 eV by increasing the rGO content. The linear trend of I–V curve suggests an ohmic contact between ZnO and rGO. Besides, it was found that by increasing the rGO content, the electrical resistivity was decreased from 4.32×10² Ω cm for pure ZnO film to 2.4×10¹ Ω cm for 0.225 wt% rGO incorporated composite film. The composite photodetectors not only possessed a desirable UV photosensitivity, but also the response time of optimum sample containing 0.075 wt% rGO was reduced to about one-half of pure ZnO thin film. Also, the calculated signal to noise (SNR) showed that highly conductive rGO in composite thin films facilitate the carrier transportation by removing the trapping centers. The mechanism of photoresponsivity improvement of composite thin films was proposed by carrier transportation process.     

Excited state interaction between Hydrochlorothiazide and europium ion in PMMA polymer and its application as optical sensor for Hydrochlorothiazide in tablet and serum samples

This paper reports on a facile technique combined with a simple, sensitive and selective spectrofluorimetric method for the determination of hydrochlorothiazide. In methanol, at pH 8.3 and λ_ex=340, hydrochlorothiazide can remarkably enhance the luminescence intensity of the Eu³⁺ ion doped in polymethylmethacrylate polymer (PMMA) matrix. This could be due to the energy transfer from hydrochlorothiazide to Eu³⁺ in the excited stated. At the optimized experimental conditions, the enhancement of the characteristic emission band (617 nm) of Eu³⁺ ion doped PMMA is directly proportional to the concentration of hydrochlorothiazide with a dynamic range of 5×10^?8–1.0×10^?5 mol L^?1 and detection limit of 8.0×10^?9 mol L^?1. Application of the suggested method was successfully applied to the determination of hydrochlorothiazide in pharmaceutical preparations and human serum samples, with high percentage of recovery, good accuracy and precision.     

Proton-conducting properties of the membranes based on poly(vinyl phosphonic acid) grafted poly(glycidyl methacrylate)

Proton-conducting properties of the graft copolymer electrolytes were examined throughout this work. The homopolymers poly(glycidyl methacrylate), PGMA and poly(vinyl phosphonic acid), PVPA were synthesized by free-radical polymerizations of the monomers glycidyl methacrylate, GMA, and vinyl phosphonic acid, VPA, respectively. The graft copolymers were produced by grafting of PVPA onto PGMA via ring opening of ethylene oxide groups. To examine the influence of the concentration of VPA on the proton conductivity, several graft copolymers were produced at various stoichiometric ratios with respect to monomer repeat units. The materials were characterized by FT-IR and ¹H NMR spectroscopy and the thermal properties were studied by thermogravimetry (TG) and differential scanning calorimetry (DSC). The TGA results demonstrated that the samples are thermally stable up to at least 150 °C. The proton conductivities of humidified and dry samples were studied via impedance spectroscopy. In the anhydrous state, the proton conductivity of P(GMA)-graft-P(VPA)₁₀ was 5 × 10^? 5 S/cm at 150 °C. The proton conductivity of the same material increased with the humidity content and reached to 0.03 S/cm at 80 °C under 50% of RH, which approached to that of Nafion^® at the same humidification level.     

Synthesis of ammonia at atmospheric pressure with Ce0.8M0.2O2−δ (M = La,Y, Gd,Sm) and their proton conduction at intermediate temperature

Ionic conduction in fluorite-type structure oxide ceramics Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) at temperature 400–800 °C was systematically studied under wet hydrogen/dry nitrogen atmosphere. On the sintered complex oxides as solid electrolyte, ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid states proton conducting cell reactor by electrochemical methods, which directly evidenced the protonic conduction in those oxides at intermediate temperature. The rate of evolution of ammonia in Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) is up to 7.2 × 10^− 9, 7.5 × 10^− 9, 7.7 × 10^− 9, 8.2 × 10^− 9 mol s^− 1 cm^− 2, respectively.     

Raman gain in modified tellurite glasses and thin films

We report the tailoring of Raman spectra of the tellurite glass by varying molar concentrations of phosphates, fluorides in phosphate modified tellurite glasses to analyze the Raman gain. From the measured Raman spectrum, the Raman gain and gain bandwidth in these glasses were calculated and compared. The structural features that give rise to the observed spectra and its dependence on glass composition are identified and reported. Raman gain as high as 170 × 10^? 13 m/W is obtained for glass modified by zinc oxide. Glass thin films prepared by pulsed laser deposition show a Raman gain of 5.0 × 10^? 13 m/W suggesting their importance in short waveguide Raman amplifier fabrication.     

Bulk and surface properties of ionic salt CsH5(PO4)2

We report a comparative study of transport and thermodynamic properties of single-crystal and polycrystalline samples of the ionic salt CsH₅(PO₄)₂ possessing a peculiar three-dimensional hydrogen-bond network. The observed potential of electrolyte decomposition ≈ 1.3 V indicates that the main charge carriers in this salt are protons. However, in spite of the high proton concentration, the conductivity appears to be rather low with a high apparent activation energy E_a ≈ 2 eV, implying that protons are strongly bound. The transport anisotropy though is not large, correlates with the crystal structure: the highest conductivity is found in the [001] direction (σ_130 °C ∼ 5.6 × 10^− 6 S cm^− 1) while the minimal conductivity is in the [100] direction (σ_130 °C ∼ 10 ⁻⁶ S cm^− 1). The conductivity of polycrystalline samples appears to exceed the bulk one by 1–3 orders of magnitude with a concomitant decrease of the activation energy (E_a ≈ 1.05 eV), which indicates that a pseudo-liquid layer with a high proton mobility is formed at the surface of grains. Infrared and Raman spectroscopy used to study the dynamics of the hydrogen-bond system in single-crystal and polycrystalline samples have confirmed the formation of such a modified surface layer in the latter. However, no bulk phase transition into the superionic disordered phase is observed in CsH₅(PO₄)₂ up to the melting point T_melt ∼ 151.6 °C, in contrast to its closest relative compound CsH₂PO₄.     

Conductivity and thermal studies of blend polymer electrolytes based on PVAc–PMMA

The polymer electrolytes comprising blend of poly(vinyl acetate) (PVAc) and poly(methylmethacrylate) (PMMA) as a host polymer and LiClO₄ as a dopant are prepared by solution casting technique. The amorphous nature of the polymer–salt complex has been confirmed by XRD analysis. The DSC thermograms show two T_g's for PVAc–PMMA blend. A decrease in T_g with the LiClO₄ content reveals the increase of segmental motion. Conductance spectra results are found to obey the Jonscher's power law and the maximum dc conductivity value is found to be 1.76 × 10^− 3 S cm^− 1 at 303 K for the blend polymer complex with 20 wt.% LiClO₄, which is suitable for the Li rechargeable batteries. The conductivity–temperature plots are found to follow an Arrhenius nature. The dc conductivity is found to increase with increase of salt concentration in the blend polymer complexes.     

Preparation of enzyme nanoparticles and studying the catalytic activity of the immobilized nanoparticles on polyethylene films

Using high-intensity ultrasound, in situ generated α-amylase nanoparticles (NPs) were immobilized on polyethylene (PE) films. The α-amylase NP-coated PE films have been characterized by E-SEM, FTIR, DLS, XPS and RBS. The PE was reacted with HNO₃ and NPs of the α-amylase were also deposited on the activated PE. The PE impregnated with α-amylase (4 μg per 1 mg PE) was used for hydrolyzing soluble potato starch to maltose. The immobilization improved the catalytic activity of α-amylase at all the reaction conditions studied. The kinetic parameters, K_m (5 and 4 g L^?1 for the regular and activated PE, respectively) and V_max (5 × 10^?7 mol ml^?1 min^?1, almost the same numbers were obtained for the regular and activated PEs) for the immobilized amylase were found to slightly favor the respective values obtained for the free enzyme (K_m = 6.6 g L^?1, V_max = 3.7 × 10^?7 mol ml^?1 min^?1). The enzyme remained bound to PE even after soaking the PE in a starch solution for 72 h and was still found to be weakly active.     

Lipase catalyzed ultrasonic synthesis of poly-4-hydroxybutyrate-co-6-hydroxyhexanoate

Four different lipases were compared for ultrasound-mediated synthesis of the biodegradable copolymer poly-4-hydroxybutyrate-co-6-hydroxyhexanoate. The copolymerization was carried out in chloroform. Of the enzymes tested, Novozym 435 exhibited the highest copolymerization rate, in fact the reaction rate was observed to increase with about 26-fold from 30 to 50 °C (7.9 × 10^?3 M s^?1), sonic power intensity of 2.6 × 10³ W m^?2 and dissipated energy of 130.4 J ml^?1. Copolymerization rates with the Candida antarctica lipase A, Candida rugosa lipase, and Lecitase Ultra? were lower at 2.4 × 10^?4, 1.3 × 10^?4 and 3.5 × 10^?4 M s^?1, respectively. The catalytic efficiency depended on the enzyme. The efficiency ranged from 4.15 × 10^?3 s^?1 M^?1 for Novozym 435–1.48 × 10^?3 s^?1 M^?1 for C. rugosa lipase. Depending on the enzyme and sonication intensity, the monomer conversion ranged from 8.2% to 48.5%. The sonication power, time and temperature were found to affect the rate of copolymerization. Increasing sonication power intensity from 1.9 × 10³ to 4.5 × 10³ W m^?2 resulted in an increased in acoustic pressure (P_a) from 3.7 × 10⁸ to 5.7 × 10⁸ N m^?2 almost 2.4–3.7 times greater than the acoustic pressure (1.5 × 10⁸ N m^?2) that is required to cause cavitation in water. A corresponding acoustic particle acceleration (a) of 9.6 × 10³–1.5 × 10⁴ m s^?2 was calculated i.e. approximately 984–1500 times greater than under the action of gravity.     

Optical properties of amorphous Si/SiO2superlattice

Amorphous Si/SiO₂(a-Si/SiO₂) superlattices have been fabricated by the magnetron sputtering technique. The superlattice with an Si layer thickness of 1.8 nm has been characterized by transmission electron microscopy (TEM). The result indicates that most of the regions in the Si layer consist of amorphous phase, while regular structure appears in some local regions. This is in agreement with the Raman scattering spectroscopy. The optical absorption spectrum and photoluminescence (PL) spectrum have been measured. Moreover, the third-order optical nonlinearity χ⁽³⁾of this superlattice has been measured. To our knowledge, this is the first investigation of the nonlinear absorption and refractive index of an a-Si/SiO₂superlattice using the Z -scan technique. The real and imaginary parts of χ⁽³⁾have been found to be 1.316  ×  10 ^− 7eus and  − 5.596  ×  10 ^− 7eus, respectively, which are about two orders of magnitude greater than those of porous silicon. The results may be attractive for potential application in electro-optics devices.     

Oxygen diffusion and surface exchange studies on (La0.75Sr0.25)0.95Cr0.5Mn0.5O3−δ

Oxygen tracer diffusion coefficient (D^⁎) and surface exchange coefficient (k^⁎) have been measured for (La_0.75Sr_0.25)_0.95Cr_0.5Mn_0.5O_3−δ using isotopic exchange and depth profiling by secondary ion mass spectrometry technique as a function of temperature (700–1000 °C) in dry oxygen and in a water vapour-forming gas mixture. The typical values of D^⁎ under oxidising and reducing conditions at ∼ 1000 °C are 4 × 10^− 10 cm² s^− 1 and 3 × 10^− 8 cm² s^− 1 respectively, whereas the values of k^⁎ under oxidising and reducing conditions at ∼ 1000 °C are 5 × 10^− 8 cm s^− 1 and 4 × 10^− 8 cm s^− 1 respectively. The apparent activation energies for D^⁎ in oxidising and reducing conditions are 0.8 eV and 1.9 eV respectively.     

1H NMR study of proton dynamics in (NH4)3H(SO4)2

Proton dynamics in (NH₄)₃H(SO₄)₂ has been studied by means of ¹H solid-state NMR. The ¹H magic-angle-spinning (MAS) NMR spectra were traced at room temperature (RT) and at Larmor frequency of 400.13 MHz. ¹H static NMR spectra were measured at 200.13 MHz in the range of 135–490 K. ¹H spin-lattice relaxation times, T₁, were measured at 200.13 and 19.65 MHz in the ranges of 135–490 and 153–456 K, respectively. The ¹H chemical shift for the acidic proton (14.7 ppm) indicates strong hydrogen bonds. In phase III, NH₄⁺ reorientation takes place; one type of NH₄⁺ ions reorients with an activation energy (E_a) of 14 kJ mol^− 1 and the inverse of a frequency factor (τ₀) of 0.85 × 10^− 14 s. In phase II, a very fast local and anisotropic motion of the acidic protons takes place. NH₄⁺ ions start to diffuse translationally, and no proton exchange is observed between NH₄⁺ ions and the acidic protons. In phase I, both NH₄⁺ ions and the acidic protons diffuse translationally. The acidic protons diffuse with parameters of E_a = 27 kJ mol^− 1 and τ₀ = 4.2 × 10^− 13 s. The translational diffusion of the acidic protons is responsible for the macroscopic proton conductivity, as the NH₄⁺ translational diffusion is slow and proton exchange between NH₄⁺ ions and the acidic protons is negligible.     

Proton dynamics in Cs3(HSO4)2(HPO4) studied by 1H NMR

Proton dynamics in Cs₃(HSO₄)₂(H₂PO₄) has been studied by means of ¹H solid-state NMR as well as thermal analyses. The thermal analysis shows an endothermic peak at 408 K, which corresponds to a superprotonic transition. Above the transition temperature a mass loss is observed in a dry atmosphere, which is easily recovered in a conventional dry atmosphere below the transition temperature. The ¹H magic-angle-spinning NMR spectra at room temperature show two peaks at 13.5 and 15.8 ppm, and a shoulder at 11.3 ppm from tetramethylsilane, demonstrating a presence of several inequivalent proton sites. Translational diffusion of protons takes place in both a room-temperature phase (RT) and a high-temperature phase (HT). In both phases reorientation of the SO₄/PO₄ tetrahedron limits the rate of the proton transport. The ¹H mean residence times are estimated as E_a = 33 kJ mol^− 1 and τ₀ = 0.97 × 10^− 9 s for phase RT from the second moment analysis and as E_a = 20 kJ mol^− 1 and τ₀ = 5.0 × 10^− 12 s for phase HT from the analysis of the ¹H T₁ results.     

Third order nonlinear optical properties of ethyltriphenylphosphonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate (III)

A novel organometallic compound, ethyltriphenylphosphonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate (III), abbreviated as TPEPADT, was synthesized. The TPEPADT doped poly(methyl methacrylate) (PMMA) thin film with a mass fraction of 1% (1 wt.%) was prepared by using a spin-coating method. The third-order nonlinear optical properties of TPEPADT in acetonitrile solution and TPEPADT-doped PMMA thin film were investigated by using the laser Z-scan technique at the wavelength 1064 nm with laser duration of 20 ps. The linear refractive index of the polymer thin film was also studied. The Z-scan curves revealed that both TPEPADT in acetonitrile solution and the polymer thin film possessed negative nonlinear refraction, exhibiting a self-defocusing effect and nonlinear absorption was negligible under the experimental conditions used. The nonlinear refractive index was calculated to be ?1.9 × 10^?18 m²/W for TPEPADT in acetonitrile solution and ?8.9 × 10^?15 m²/W for the polymer thin film. These results suggest that TPEPADT have potential for the application of all-optical switching devices.     

Effect of oxygen partial pressure on the structure and properties of Cu–Al–O thin films

We have studied the electrical and optical properties of Cu–Al–O films deposited on silicon and quartz substrates by using radio frequency (RF) magnetron sputtering method under varied oxygen partial pressure P_O. The results indicate that P_O plays a critical role in the final phase constitution and microstructure of the films, and thus affects the electrical resistivity and optical transmittance significantly. The electrical resistivity increases with the increase of P_O from 2.4 × 10^?4 mbar to 7.5 × 10^?4 mbar and afterwards it decreases with further increasing P_O up to 1.7 × 10^?3 mbar. The optical transmittance in visible region increases with the increase of P_O and obtains the maximum of 65% when P_O is 1.7 × 10^?3 mbar. The corresponding direct band gap is 3.45 eV.     

Intrinsic pinning properties of FeSe0.5Te0.5

The intrinsic pinning properties of FeSe_0.5Te_0.5, which is a superconductor with a critical temperature T_c of approximately 14 K, were studied through the analysis of magnetization curves obtained using an extended critical state model. For the magnetization measurements carried out with a superconducting quantum interference device (SQUID), external magnetic fields were applied parallel and perpendicular to the c-axis of the sample. The critical current density J_c under the perpendicular magnetic field of 1 T was estimated using the Kimishima model to be equal to approximately 1.6 × 10⁴, 8.8 × 10³, 4.1 × 10³, and 1.5 × 10³ A/cm² at 5, 7, 9, and 11 K, respectively. Furthermore, the temperature dependence of J_c was fitted to the exponential law of J_c(0) × exp(?αT/T_c) up to 9 K and the power law of J_c(0) × (1 ? T/T_c)ⁿ near T_c.     

Quick response PZT/P(VDF-TrFE) composite film pyroelectric infrared sensor with patterned polyimide thermal isolation layer

The fabrication method and the pyroelectric response of a single element infrared sensor based lead zirconate titanate (PZT) particles and polyvinylidene fluoride P(VDF-TrFE) copolymer composite thick film is reported in this paper. A special thermal insulation structure, including polyimide (PI) thermal insulation layer and thermal insulation tanks, was used in this device. The thermal insulation tanks were fabricated by laser micro-etching technique. Voltage responsivity (R_V), noise voltage (V_noise), noise equivalent power (NEP), and detectivity (D^*) of the PZT/P(VDF-TrFE) based infrared sensor are 1.2 × 10³ V/W, 1.25 × 10⁻⁶ V Hz^1/2, 1.1 × 10⁻⁹ W and 1.9 × 10⁸ cm Hz^1/2 W⁻¹ at 137.3 Hz modulation frequency, respectively. The thermal time constant of the infrared sensor τ_T was about 15 ms. The results demonstrate that the composite infrared sensor show a high detectivity at high chopper frequency, which is an essential advantage in infrared detectors and some other devices.